Metal coated fibers and treatments therefor



June 26, H. w n-E s-r METAL COATED FIBERS AND TREATMENTS THEREFOROriginal Filed March 30, 1954 LUBRICANT METALLIC SOAP METAL COATING(ox/0E) GLASS FIBER GLASS FIBER LUBRICANT REACTION PRODUCT METAL COATINGGLASS FIBER GLASS FIBER Fig.5 1;"; 6

IN VEN TOR. HARRY B. WHITEHURST ATTORNEYS 3,941,202 Patented June 26,1962 Fla 3,641,202 METAL CGATED FlfiEllS AND TREATMENTS THEREFOR HarryB. Whitehurst, Newark, Qhio, assignor to wens- Corning FiherglasCorporation, a corporation of Delaware Original application Mar. 30,1954, Ser. No. 419,920, now Patent No. 2,920,981, dated Jan. 12, 196i}.Divided and this application Dec. 29, 1958, Ser. No. 78$),fi95

12 Claims. (Cl. 117-71) This application is a division of my copendingapplication having Serial Number 419,920, filed March 30, 1954, now U.8. Patent 2,920,981.

This invention relates to metal coated fibers and particularly to metalcoated fibrous glass and treatments for enhancing the propertiesthereof.

In an attempt to adapt fibrous glass for certain new uses, the fibershave been coated with metals and alloys of metals such as have beendescribed in copending applications. One or more of the following metalsand alloys are applied by a suitable method as disclosed in copendingapplications having Serial Numbers 380,868, new Pat. No. 2,979,424;398,544, now abandoned; 317,678, new abandoned; 318,786, now Pat. No.2,928,716; 319,388, now Pat. No. 2,772,987; 391,184, new Pat. No.2,848,390; 399,239, now Pat. No. 2,980,956: lead, zinc, tin, copper,aluminum, silver, Woods alloy, Roses alloy, and various other alloyssuch as zinc-titanium, lead-copper, lead-tin, aluminum-copper,aluminum-gold, aluminum-zinc, aluminum-tin, lead-antimony, cadmium-zinc,copper-cadmium, tin-indium, silver-tin, silver-zinc, copper-zinc,antimony-tin, antimony-zinc, copper-aluminum, Dow metal, brazing andsoldering alloys and the like. Metal coated fibers having secondary andtertiary coatings of electrodeposited metal are likewise treated by themethods and materials of this invention. In order to facilitateprocessing of metal coated fibers, it has been found necessary to treatthe fibers with various agents to provide handleability. Treatments forbare fibrous glass used in the textile arts have been described in theliterature and generally comprise the application of size and bindercompositions and the like. Some of these compositions are adapted foruse with metal coated fibrous glass; however, a number of treatmentsespecially suited for metal coated fibrous glass have been discovered.

It is an object of this invention to provide treatments for enhancingthe properties of metal coated fibers.

'It is an object to provide novel decorative effects on fibrous glassand products thereof.

It is an object to reduce the coefiicient of friction of metal surfacesof fibers which slide one over the other.

It is a further object to provide methods of improving the physicalproperties and handling characteristics of metal coated fibrous glass inthe form of textile materials.

It is an object to provide surface protective coatings for metal coatedfibers.

The objects of this invention are attained by treating metal coatedfibers with specific materials within the classification of lubricants,sizes, coating materials, acids, bases, oxidizing agents, adhesives ormixtures of one or more of these materials.

To improve the handling characteristics of metal coated fibers which areto be used in reinforcing other materials, it is necessary to grouptogether a sufficient number of fibers in the form of a strand, yarn,roving or the like in order to obtain sufficient bulkiness so that thestrand or other form can be handled in processing steps which follow theforming operation, i.e., twisting, plying and so forth. If a strandcomprising a plurality of fibers is to be handled, it is generallynecessary that some sort of a size or lubricating material be applied toprovide strand integrity. The treating material must hold togetherindividual fibers within a single strand with sufficient strength toprovide integrity. However, adjacent strands should not be so firmlyadhered one to another within a package that the package cannot beunwound.

It has been found that various lubricants may be used to treat thefibers or strands or yarns of fibers which have been metal coated.Application of a lubricant reduces the number of broken fibers in thestrand and tends to hold any broken fibers adjacent to unbroken fibersin the strand and thereby provides strand integrity. Lubricants may beapplied to the individual fibers as they are being formed but beforethey are gathered into a strand or they may be applied to the strand,cord, yarn or bundle of f1- bers during subsequent steps in the processof producing textile materials. Lubricants fall generally into one ofseveral classes including liquid metals, various organic materials,metal films, inorganic materials, oils with or without additives and thelike.

Included with the organic materials used as lubricants are thosematerials such as parafiin oil, solid hydrocarbons, tetrafiuoroethylene,polyethylene, polystyrene, liquid fatty acids and the like. The fattyacids which may be used in treating metal coated fibrous glass includeacetic, propionic, valeric, caproic, pelargonic, capric, lauric,myristic, palmitic, stearic and others. Such paraffins as nonane,decane, hexadecane, docosane and triacontane may be used. The alcoholswhich may be used include butyl, octyl, decanol and cetyl alcohol. Anyof these organic materials may be applied by themselves or in mixturessuch as in water dispersions or solutions or in solution in varioussolvents.

Fatty acids are especially adapted for application to metal coatedfibers. The fatty acids listed above and preferably lauric or stearicacid are applied in combination with parafiin oil to provide a surfacehaving a low coefi'icient of friction which is desirable for improvingflex life and handling characteristics of fibers in the form of a strandor yarn.

Liquid metals such as mercury may be applied in minute quantities toprovide a marked reduction in friction when silver coated fibers slideover adjacent silver coated fibers. The mercury wets the silver andforms an amalgam which acts as a lubricating surface.

Thin metal films may be formed upon the thicker coating of metal alreadyon the fibers to provide a lubricant layer which gives longer flex lifeand improved strength.

For instance, a thick silver coat may first be applied to the fibrousglass and then a relatively thinner deposit of lead or lead-tin orlead-indium alloy provides a metal film which lubricates the fibers. Athin film of copper can be formed upon a zinc coated fiber by includinga small proportion of copper-sulfate in a size or treating solutionwhich is applied to the zinc coated fiber. Replacement of part of thezinc with copper takes place. The copper-sulfate may be applied alongwith any conventional size such as a gelatine or starch size whichincludes wetting and emulsifying agents.

Conventional fibrous glass sizes are well adapted for treating metalcoated fibers to provide the desired lubricity. The sizes used on barefibrous glass include those having generally the following ingredients:a film former such as polyvinyl acetate or gelatine, a suitablelubricant, emulsifying and Wetting agents and a liquid carrier which ispreferably water. Water systems are generally preferred over solventsystems, since they are less expensive, less toxic and less dangerous.

Certain inorganic materials provide the lubricity necessary forimproving handling characteristics, integrity and other physicalproperties of metal coated fibers in the form of strands or yarns.Finely divided carbon, graphite, rnolybdenum disulfide and micadispersed in suitable liquid carriers including oils, various petroleumfractions, water and the like are applied to provide a low frictionsurface. All of these materials provide a low coefficient of friction onthe metal surface so that the llex life and the handling characteristicsare greatly improved. The liquid component of the dispersion may be asize or hinder composition.

Oils may be applied including those classified as mineral, vegetable andanimal oils. The mineral oils are especially adapted for application tometal coated fibers and certain materials which are classified asadditives for oils are included in the treating materials for metalcoated fibers. Long chain organic polymers including polybutcnes,polyethyleues, vinyl polymers, polystyrenes and methacrylatcs may beadded and the silicone materials including the short chain and ringpolymers may be added to enhance the lubricating properties provided bythe oils themselves.

Certain fiuorolubes such as tetrafiuoroethylene may be applied to themetal coated fibers either in a finely divided state or by passing themetal coated fiber or strand over a rod of tetrafiuoroethylene while themetal coated fiber or strand is at an elevated temperature.

Chlorolubes may likewise be applied to the metal coated fibers as mayother halogenated compounds. For instance, ethyl benzene which has beenchlorinated under intense ultraviolet light may be applied to metalcoated fibers to provide lubrication.

It has also been found beneficial to form metal soaps in situ upon themetal coated fibers or groups of fibers by application of a fatty acidto the metal surface and then heating. One percent lauric acid inparafiln oil is applied to the metal coated fibers at an elevatedtemperature. A hot bath of the parafiin oil is preferably used althoughthe metal coated fiber may be at an elevated temperature also. Reactivemetals such as copper, cadmium and zinc form metallic soaps which arevery good lubricants. The metal soap and not the fatty acid provides thelubricity in this instance.

Various lubricants can be used for treating the metal coated fibers;however, specific embodiments of the invention which relate to forming areaction product on or with the metal surface are illustrated in thefollowing drawing wherein:

FIGURE 1 shows an exaggerated view of a glass fiber with metal and metalsoap coatings;

FIGURE 2 depicts a glass fiber with an etched metal coating and a metalovercoat;

FIGURE 3 shows a glass fiber with a metallic soap coating;

FIGURE 4 illustrates a glass fiber having an oxidized metal coating anda lubricant on the metal oxide surface;

FIGURE 5 shows a glass fiber with a metal coating and a lubricantthereovcr; and

FIGURE 6 shows a glass fiber with a coating of a reaction product on thesurface.

Although metal soaps formed in situ are greatly preferred since they arelinked to the metal surface, metallic soaps as such are applicable inparafin oil. For instance, one percent cadmium mercapto-palinitate inparaffin oil is applied to fibers coated with cadmium with a greatlyreduced coefficient of friction resulL ng. Likewise, cadmium stearate,copper laurate, Zinc laurate, or copper stcaratc may be applied tolubricate metal coated fibers. Soaps which are applied as such breakdown at lower temperatures than the softening point of the soap due totheir increased solubility in the paraffin oil at elevated temperatureand the weak attachment to the metal. Metallic soaps formed in situ aremore firmly attached to the metal surface and can withstand appreciabledeformation so that they are very protective to toe surface.

Fatty acid esters are applied to metal coated glass surfaces to providelow friction surfaces. These esters react with the base metal to form afatty acid by hydrolysis. For instance, ethyl stearate in a dilutebenzene solution is applied to the metal coated fibers and by hydrolysisa small amount of fatty acid is formed which attacks the metal surfaceforming the. metal stearate or other metal soap corresponding to thefatty acid ester used. These esters can lubricate metal surfaces attemperatures greater than the melting point of the ester itself. Othersolvents than benzene which may be used with ethyl stearate includecyclohexanc, octane and hexane.

It is believed that treating a me-.. surface with a fatty acid forms amonolayer which is relatively thin and wherein the acid chain isoriented so that it is norina to the surface of the metal provided theacid chain contains twelve or more carbons. Probably eight carbons areenough to provide the oriented, perpendicular chains if the metalsurface is one of the reactive metals. The layers on top of thismonolayer crystallize into typical crystalline forms of fatty acid andthe hydrocarbon chains therein are inclined at an appreciable angle tothe surface normal. These first monolayers are more firmly attached andit is believed that they are the most effective lubricating andprotective means.

it has been noted that water and oxygen must be present before the metalis lubricated by the fatty acids such as lauric acid used as a onepercent solution in paraffin oil. Clean metal surfaces are notlubricated and those subjected to air alone are generally notlubricated. Air saturated with water is believed to be necessary inorder to provide an oxide film with which the fatty acid reacts to formthe metal soap. The fatty acid soaps can be formed with magnesium,cadmium, zinc, copper, iron, aluminum and the like.

Phosphide protective films provide lubrication for metal coated fibers.Tricresyl phosphate reacts with metal to form phosphides which affectthe frictional properties of the metal surfaces. One and one-halfpercent of tricresyl phosphate in white mineral oil is applied to metalcoated fibers to provide a reduction in friction. Tricresyl phosphatemay also be applied by including it as one of the ingredients in aconventional size or lubricating material. Very small proportions oftricresyl phosphate in the order of one percent or two percent or lessprovide the desired phosphide layer. Tricresyl phosphate is also appliedalong with either copper oleate or mesityl heptadecyl ketone in whiteoil.

Chloride and sulfide protective films likewise provide good lubrication.Copper or cadmium coated fibers which are exposed to dry chlorine gasand then covered with paraffin oil to protect the relatively thick coatof chloride have good lubricating properties. Ammonium polysulfidesolution is used to treat metal surfaces to form a sulfide layer andthen paraffin oil and better yet paralfin oil having a small percentageof fatty acid is used to protect the sulfide layer. A dilute solution ofsodium sulfide may be used instead of the ammonium polysulfide to formthe sulfide film. These sulfide layers provide low coefficients offriction up to C. or higher.

Certain long chain paraffinic halides including octadecyl chloride,cetyl bromide and cetyl iodide may likewise be used to treat metalcoated fibrous glass in order to improve the lubricity thereof.

Long chain acid chlorides, such as stearyl chloride applied in dilutesolution in paraffin oil, provide low friction with metals even at 275C. or higher.

A 0.1 percent solution of BB dichlor dicetyl selenium dichloride isapplied to metal coated fibers and then heated to about C. Thislubricant provides a large reduction in friction. One percent of B,B'dichlor dicetyl selenium dichloride and one percent of stearic acid inparafiin oil is applied to metal coated fibers to provide a largereduction in friction. Other compounds containing the selenium chloridegroup seem to give like results. These materials are good for use withcopper and cadmium coated fibers of glass.

Sulfurized oleic acid and sulfurized cetene may be appliedadvantageously to metal coated fibers such as silver coated fibers toreduce materially the coefficient of friction between the metalsurfaces. These materials provide a low coefficient of friction betweenadjacent fibers within a strand over a wide range of temperatures, i.e.,from about 20 to 300 C.

Pure long chain sulfur compounds containing a replaceable hydrogen atomsuch as cetyl mercaptan, cetyl sulfonic acid di-thio tridecylic acid,alpha mercapto palmitic acid and the like provide lubrication on copperand cadmium coatings on fibrous glass.

It is desirable to improve the tensile strength of the final cord orstrand by a tensioning treatment after applying one of the abovedisclosed lubricants. The individual metal coated fibers are aligned andcompacted by such means, the alignment and orientation of the fibersbeing facilitated by the presence of a suitable lubricant on the surfaceof the fibers. After the fibers are aligned, each of them is in aposition to carry its share of any load which may be imposed on the cordor strand.

In order to lower the coefiicient of friction, it is desirable to forman outer layer of oxide upon the metal coated fibers. The coefiicient offriction is reduced when the metal surface is allowed to form an oxide;therefore, it is desirable in certain instances to direct oxygen to themetal coated surface which has been newly formed in order to acceleratethe oxidation. The fibers having oxidized surfaces may be used as formedor may be further treated with lubricants or other coatings. Anodizingof aluminum surfaces provides decorative oxide coatings on fibrousglass. Oxidation of other metals by electrochemical methods providesbeneficial properties. Oxidation of copper coatings has providedincreased flex life for fibers.

Acids or bases may be used for treating the metal sur faces of fibers.For instance, a mineral acid may be used for etching a metal coatedfiber. Chromium is etched with dilute sulfuric acid to form pocketswhich are suitable for holding a lubricant such as mineral oil or thelike. This oil provides boundary lubrication when adjacent fibers withina strand rub together. It is desirable in other instances to etch themetal surface in order to form small nodules upon the metal surface tomaterially reduce the contact area between adjacent contacting fibers.After etching, it is desirable in some instances to coat the etchedsurface with the same or an unlike metal. The second metal is preferablya hard metal such as chromium.

The application of secondary coatings of metal by electrodeposition orother suitable means onto the metal coated fibers is desirable in orderto provide a strong underlying body of metal over which lies a thin filmof a metal that acts as a lubricant. For instance, chromium and rhodiumgive exceptionally good frictional resistance, and for this reason, areespecially adapted as coating materials for other metal undercoats suchas aluminum, nickel, zinc and others.

Various textile sizes are used in treating metal coated fibers andfibrous products. A size comprising about five percent gelatine, fivepercent vegetable oil or animal oil, a small proportion of emulsifyingagent and the remainder being Water is well adapted for treating metalcoated fibers within a strand to provide integrity and good handlingcharacteristics.

The disclosed lubricants including the organic materials such as theliquid fatty acids, the inorganic materials including graphite and thelike, the oils including the mineral oils and the silicones etc., thechlorolubes and fluorolubes, the metal soaps and the like may be addedto size materials which act as the carrier, the lubricants being anadditive or a major ingredient as may be desired.

Other fibrous glass textile sizes having as an ingredient such materialsas synthetic latices, polyamides, vinyl polymers, siloxanolates,silicones, tetrafluoroethylene, methacrylato chromic chloride, stearatochromic chloride and others may be used as the carrier for thelubricants disclosed. Generally the sizes used are water systems;however, solvent systems may be used.

Certain sizes have been found to be especially adapted for givingintegrity to metal coated strand.

A size comprising one-half percent dodecyl amine acetate and one-halfpercent gelatine is applied to metal coated fibers in the formingoperation. This size allows unwrapping of the packages of strand formedof the metal coated fibers without attendant ringers caused by fiberswhich become detached from the strand and snarls caused by broken fibersprotruding from the strand. A small quantity of 0.01 N or 0.001 N coppersulfate may be added to the above size in order to replace part of themetal already deposited on the glass. For instance, zinc coated fiberscan be provided with a very thin outer film of copper by including asmall proportion of copper sulfate in the size.

A size comprising the following ingredients by Weight is used intreating zinc coated fibers:

Example I Ingredient Proportion,

Percent Range Gelatine O Polyethylene glycol (Carbowax 1500) 0.Propylene glycol 0.

ater 99.

The propylene glycol may be replaced with other humectants such asglycerine or any suitable glycol. The water is necessary in order toplasticize the gelatine so that the gelatine does not form a hard cakewhich hinders unwinding of the package.

The following sizes have been applied to 102 filament strands coatedpreviously with zinc or zinc alloy.

Remainder water.

These sizes are very satisfactory for the purposes of this invention andit should be understood that they may be used with various other metalsthan zinc with equally good results.

Various other coatings may be applied to the metal coated fiber when thefiber or strand is to be combined with materials such as resins, rubberand the like. Certain size compositions are applied to give strandintegrity and good handle-ability as disclosed. To the size compositionsmay be added other dispersions of resin-like or rubbery polymerizationproducts obtained by polymerizing monomeric materials such asbutadiene-1,3, isoprene, 2- chlorobutadiene-1,3, isobutylene orinterpolymers of these monomers with interpolymerizable monomers such asstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, methylacrylate, ethyl methacrylate, 2-vinyl pyridine, and others.

Butadiene-styrene copolymers are generally rubbery but copolymers highin styrene (styrene-butadiene copoly- 7 mers) tend to be tougher andmore resin-like. Either the resin-like or rubber-like compounds may beused as additives for the size compositions.

Resinous products such as phenol formaldehyde may likewise be added tothe size compositions, preferably in the form of finely divideddispersions.

Metal coated fibers or bundles of fibers which may or may not have beentreated with a size are coated with adhesive compositions before theyare combined with rubber, resin or other materials which are to bereinforced. Rubber adhesives comprising a rubbery component and aresinous component in solvent systems are utilized to treat metal coatedfibers before they are combined with rubber to produce glass reinforcedrubber products. Conventional rubber adhesives comprisingresorcinol-formaldehyde latex are used likewise to achieve the desiredbonding effect between the reinforcing fibers and the body or carcass ofrubber.

Rubber adhesives are readily applied by dipping the metal coated fiberin a latex or cement bath or by spreading a cement bath upon a fabricwoven of metal coated fibers. The cement which comprises compoundedrubber in an organic solvent is directed upon the surface of a wovenfabric or a weftless fabric and the excess removed by a doctor blade.The cement is then dried by applying heat to remove the solvent.

A strand or a cord comprising metal coated fibrous glass when passedthrough an adhesive bath picks up sufficient adhesive to fill theinterstices of the strand and provide a coating over the strand itself.The rubbery component of the adhesive may be vulcanized at the same timethat the glass reinforced rubber product is vulcanized or molded.

Adhesive compositions comprising natural rubber latex, caustic potash,zinc oxide, sulfur and suitable accelerators and the like are used totreat metal coated fibers and these fibers are then combined with rubberby calendering methods or other suitable means and the resulting productis heated for a sufiicient time to effect vulcanization of the rubber inthe adhesive and that in the body or carcass of the glass-reinforcedrubber product.

Chloroprene latex adhesives comprising zinc oxide, accelerator andneoprene latex likewise may be used.

Good adhesion of metal coated fibers to rubber during vulcanization isalso achieved as follows. To the metal coated fibers is applied a metalto rubber adhesive such as Ty Ply Q which is a chemical derivative ofrubber dispersed in a volatile solvent. The coated metal is thencombined with a suitable sheet of natural or reclaimed rubber and thecomposite product is heated in a mold under pressure to vulcanize therubber.

Chloroprene and butadiene-acrylonitrile rubbers are bonded to metalcoated fibers during vulcanization by using Ty Ply S which is likewise achemical derivative of rubber in volatile solvents. Ty Ply S is adaptedfor use with synthetic rubber.

Metal coated fibers are provided with an outer coating of rubber byelectrodepositing rubber thereon by the Sheppard process disclosed inUnited States Patents 1,589,324 to 1,589,330, inclusive, and others.Rubber is electrodeposited on lead, cadmium, zinc, tin, antimony andalloys of these metals which has been applied to fibrous glass bypassing the metal coated fibers through an electroplating bathcomprising the following ingredients.

Rubber so deposited has great strength. Fibers so treated are readilycombined with rubber in the carcass of a tire, belt or other rubberproduct.

The metal coating imparts abrasion resistance and greater strength tothe fibrous glass and the electrodeposited outer rubber coating which isvery strong adds further to the abrasion resistance of the individualfibers and provides an outer surface on fibers, strands, cords, bundlesof fibers or fabrics which is very compatible with rubber. Metal coatedfibers having an .outer layer of electrodeposited rubber are combinedwith a rubber carcass by conventional methods such as by applyingsuitable rubber adhesives to the rubber surfaces to be joined followedby a vulcanization step.

When iron or iron alloys are used to coat the fibrous glass, surfacetreatments such as nitriding, phosphiding or sulfurizing or combinationsof these processes may be used to provide additional surface hardness orother improved physical properties.

Metal coated fibers are provided with an outer coating of plasticizedvinyl polymers such as polyvinyl chloride and the like using calenderingor extruding processes. Metal coated fibers are coated with plastisols,highly plasticized vinyl polymers, by drawing the fibers through a bathof plastisol and then stripping the excess plastisol by passing thefiber through a die. Solvent solutions of vinyl polymers may be appliedby dipping or other coating processes also. Strands, bundles of fibers,yarns or the like may be so treated.

Metal coated fibers are dyed by coating the fibers with a metal such asaluminum, chromium, iron, tin, antimony, copper or any other metal whichforms soluble salts. A salt of the metal is then produced by treatingthe metal coat with the appropriate acid and this metal salt is reactedwith a mordant dye to form an insoluble metal compound upon the surfaceof the fiber.

Various other treatments for metal coated fibers are included within thespirit and scope of the appended claims.

We claim:

1. A method of treating metal coated fibrous glass comprising applying1.5 percent tricresyl phosphate in white mineral oil to form a metalphosphide which reduces surface friction and adds a lubricant.

2. Method of providing a protective film on metal coated fibrous glasscomprising exposing said fibers to dry chlorine gas to form a metalchloride and then applying parraffin oil to the chloride coating soformed.

3. Method of providing a protective film on metal coated fibrous glasscomprising applying ammonium polysul-fide solution to the metal surfaceto form a metal sulfide layer and applying paraffin oil to the metalsulfide layer.

4. Method of treating metal coated fibrous glass comprising applying anetching acid thereto to provide a roughened surface, removing the excessacid, and applying a second coating of metal upon said roughenedsurface, which second coating acts as a lubricant.

5. The method of claim 4 wherein the second coating of metal ischromium.

6. Method of treating metal coated fibrous glass comprising applying anetching acid thereto to provide a modified surface, removing the excessacid, and applying a lubricant to the modified surface.

7. Method of treating metal coated fibrous glass com prising applying anetching acid thereto to provide a modified surface, removing the excessacid, and applying mineral oil to the modified surface as a lubricant.

8. Method of treating metal coated glass fibers comprising reacting themetal coated glass fibers with a reactant which modifies the metalsurfaces and applying a dispersion of a material from the groupconsisting of carbon, graphite, molybdenum disulfide,tetrafluoroethylene, and mica as a lubricant.

9. Method of treating metal coated glass fibers comprising reacting themetal coated glass fibers with a react-ant which modifies the metalsurfaces and applying tricresyl phosphate in a liquid carrier to themodified surfaces as a lubricant.

10. Method of treating metal coated glass fibers comprising reacting themetal coated glass fibers with a reactant which modifies the metalsurfaces and applying a long chain parafiinic halide to the modifiedsurfaces as a lubricant.

11. Method of treating metal coated glass fibers comprising reacting themetal coated glass fibers with a reactant which modifies the metalsurfaces and applying one percent of B,B' dichlor dicetyl seleniumdichloride and one percent of stearic acid in parafiin oil to themodified surfaces as a lubricant.

12. Method of treating metal coated glass fibers comprising reacting themetal coated glass fibers with a reactant which modifies the metalsurfaces and applying 10 a long chain sulfur compound containing areplaceable hydrogen atom of the group consisting of cetyl mercaptan,cetyl sulfonic acid, di-thio tridecylic acid, and alpha mercaptopalmitic acid to the modified surfaces as a lubricant.

References Cited in the file of this patent UNITED STATES PATENTS2,481,372 Von Fuchs Sept. 6, 1949 2,662,836 Montgomery et al Dec. 15,1953 2,707,157 Stanton et a1 Apr. 26, 1955 2,772,518 Whitehurst et a1.Dec. 4, 1956 2,782,563 Russell Feb. 26, 1957 2,848,390 Whitehurst et a1.Aug. 19, 1958 2,849,107 Logue Aug. 26, 1958 2,930,105 Budd Mar. 29, 1960

8. METHOD OF TREATING METAL COATED GLASS FIBERS COMPRISING REACTING THEMETAL COATED GLASS FIBERS WITH A REACTANT WHICH MODIFIES THE METALSURFACES AND APPLYING A DISPERSION OF A MATERIAL FROM THE GROUPCONSISTING OF CARBON, GRAPHITE, MOLYBDENUM DISULFIDE,TETRAFLUOROETHYLENE, AND MICA AS A LUBRICANT.